Azo dyestuffs containing a 2-organo sulfonylbenzothiazole group



United States Patent Q many, assignors to Farbenfabriken Bayer Aktiengesellschaft, Leverkusen,

Germany No Drawing. Filed May 18, 1966, Ser. No. 550,915

Claims priority, application (germany, May 24, 1965,

Int. Cl. C09b 45/28; Dil6p 1/10; C07d 91/44 US. Cl. 260-145 6 Claims Germany, a corporation of ABSTRACT OF THE DISCLOSURE A dyestuff of the formula wherein A stands for the residue of a coupling component, R is hydrogen or a substituent, R is an aliphatic, carbocyclic, or heterocyclic substituent, and n is a number ranging from 1 to 2. The dyestuffs are useful in the dyeing of especially natural and regenerated cellulose textiles as well as those of wool, silk, polyamides, and polyurethanes with excellent fastness to wet processing.

The present invention relates to valuable new reactive dyestuffs of the general structure In this formula A denotes the radical of an azo component, R is hydrogen or a substituent, R is an aliphatic, carbocyclic or heterocyclic radical and n is a number of l to 2.

Suitable reactive substituents SO R in the 2-position of the benzothiazole ring are, inter alia, lower alkylsulphonyl radicals, preferably with 1 to 5 carbon atoms, such as methylsulphonyl, ethylsulphonyl or propylsulphonyl radicals; arylsulphonyl radicals, such as phenylsulphonyl, p-toluene-sulphonyl, p-chlorophenylsulphonyl, In carboxyphenylsulphonyl radicals; aralkylsulphonyl radicals, such as benzylsulphonyl anrd p-toluylmethylsulphonyl radicals; and also heterosulphonyl radicals, such as 2-benzothiazole-sulphonyl.

Examples of substituents R are: alkyl, aryl and aralkyl radicals, sulphonic acid, carboxylic acid, halogen substituents, such as chlorine and bromine substituents, furthermore hydroxy, alkoxy, cyano groups and sulphonarnide groups which may be substituted.

Dependent upon the type of their substituents, the new dyestuffs of Formula I may be water-soluble as well as hardly soluble or insoluble in water.

The azo component A may contain the substituents customary for dyestuffs, such as sulphonic acid, carboxylic acid, optionally substituted sulphonamide, sulphone, alkylamino, aralkylamino, arylamino, acylamino, nitro, cyano, halogen, hydroxyl, alkoxy, azo, azoporphin groupings and the like. The dyestuffs may moreover contain further groupings capable of fixation, such as mono-, dior trihalopyrimidinyl-amino, monoor di-triazinyl-amino, es-

3,480,61 l Patented Nov. 25, 1969 terified sulphonic acid-hydroxyalkyl amide and -hydroxyalkylsulphone groups and other reactive groups which are known in large numbers.

The new dyestuffs can be metal-free or metal-containing and they may be monoor polyazo dyestuffs.

Diazo components, suitable for the manufacture of the novel dyestuffs of the benz-othiazole series of the formula which contain a reactive sulphonyl substituent in the 2- position are, for example:

7-amino-2-methylsulphonyl-benzothiazo1e 6-amino-2-methylsulphonyl-benzothiazole S-amino-2-methylsu1phonyl-benzothiazole 4-amino-2-methylsulphonyl-benzothiazo'le 5-amino-6-methyl-2-methylsulphonyl-be'nzothiazole 6-amin-o-7-methyl-2-methylsulphonyl-benzothiazole 5-amino-6-chloro-2-methylsulphonyl-benzothiazole 5 -amino-6-methoxy-2-methylsulphonyl-benzothiazole 6-amino-4-sulpho-2-methylsulphonyl-benzothiazole 6-amino-5-sulpho-2-methylsulphonyl-benzothiazole 6-amino-7-sulpho-2-methylsulphonyl-benzothiazole 6-amino-2-(4'-tolylsulphony1) -benzothiazole 6'amino-5-chloro-2-methylsulphonyl-benzothiazole 6-amino-5-methoxy-Z-methylsulphonyl-benzothiazole 6-amino-5-methyl-2-methy1sulphonyl-be-nzothiazole 4-amino-6-methyl-Z-methylsulphonyl-benzothiazole 4-amino-6-methoxy-Z-methylsulphonyl-benzothiazole 4-amino-6-chloro-2-methylsulphonyl-benzothiazole In the range of the said classes of dyestuffs, the dyestuffs of the following general Formulae II to XI are especially valuable, inter alia:

in which B stands for hydrogen, alkoxy or an acylamino or arylamino substituent, u for a number of 1 to 3, R and R have the meaning stated above.

(SOaH) t (III) in which X stands for O or 'HN, C for hydrogen or a substituent, such as chlorine, bromine or alkyl, R and R have the meaning stated above, t stands for 1 or 2.

in which D stands for hydrogen, a hydroxyl or acylamino group, R, R and thave the meaning stated above.

in which E stands for the radical of a diazo component, preferably of the benzene or naphthalene series, R, R and t have the meaning stated above.

N Cu in which F stands for a phenyl radical which is substituted by one or more sulphonic acid groups and in which the azo and O groupings stand in o-position to one another, and R and R have the meaning stated above.

(VII) in which G denotes an acyl group, K and K stand for hydrogen or a substituent, such as methyl, methoxy, an

acylamino group or a w-methane-sulphonic acid group.

R1 I O-Cu--O (VIII) RSO in which R, R B, K and u have the meaning stated above.

in which E stands for the radical of a diazo component, preferably of the benzene or naphthalene series, R, R and t 'have the meaning stated above.

in which Z denotes a hydroxyl group, R, R and t have the meaning stated above.

in which R, R B and u have the meaning stated above.

Among the dyestuffs of the Formulae I to XI those are of particular interest in which the azo grouping stands in the 5- or 6-position of the benzene ring of the benzothiazole component.

The new dyestuffs of the Formula I are obtained, when diazotised aminobenzothiazoles of the formula are coupled with the coupling components in a mineral acid, acetic acid, neutral or soda-alkaline medium, depending on the coupling component employed. Preferred azo components are those of the series of aminobenzenes, hydroxybenzenes, hydroxynaphthalenes, aminonaphthalenes, pyrazolenes, aminopyrazoles and acetic acid amides. Of the large number of suitable azo components, the following compounds may be mentioned by way of example: 1-amino-3-methy1-benzene, 1amino-3-methyl-6-methoxybenzene, l-amino-benzene-3-sulphoacetylamino-benzene,

resorcinol, 1amino-benzene-3-w-methane-sulphonic acid, 1hydroxynaphthalene-4-sulphonic acid, 1-hydr0Xynaphthalene-4,S-disulphonic acid 1-hydroXynaphthalene-3,6-disulphonic acid 1hydroxynaphthalene-4,7-disulphonic acid 1-hydroXynaphthalene-3,S-disulphonic acid l-hydroxynaphthalene-B,6,8-trisulphonic acid 2-hydroxynaphthalene-3,6-disulphonic acid 2-hydroxynaphthalene-6,8-disulphonic acid Z-hydroxynaphthalene-5,7-disulphonic acid 2-hydroxynaphthalene-6-sulphonic acid 2-hydroxynaphthalene-S-sulphonic acid 1-amino-naphthalene-6,7 and 8-sulphonic acid Z-amino-naphthalene-Ssulphonic acid Z-amino-naphthalene-5,7-disulphonic acid 1,3dihydroxynaphthalene-5,7-disulpl1onic acid 1hydroxy-8acetamino-naphthalene-3,6-disulphonic acid 1hydroxy-8-acetamino-naphthalene-3,S-disulphonic acid 1hydroxy-8-benzoylamino-naphthalene-3,5-disulphonic acid 1hydroxy-8benzoylaminonaphthalene-3,6-disulphonic acid 1hydroxy-8-aminonaphthalene-3,6-disulphonic acid 1hydroxy-Samino-naphthalene-3,5-disulphonic acid 1hydroxy-7-amino-naphthalene-3,6-disulphonic acid 1hydroxy-7-amino-naphthalene-3sulphonic acid 1hydroxy-6-amino-naphthalene-3sulphonic acid 1hydroxy-6-amino-naphthalene-3,S-disulphonic acid 1-hydroXy-7- (3 -sulphophenyl-) amino-n aphthalene-3- sulphonic acid 1-hydroxy-6- 4-su1phophenyl-) amino-n a phthalene-3- sulphonic acid 1hydroxy-6-acetamino-naphthalene-3sulphonic acid 1hydroxy-8amino-naphthalene-5,7-disulphonic acid 1hydroxy-8acetamino-naphthalene-S-sulphonic acid 1- (4'-sulphophenyl-) pyrazolone-S-carboxylic acid-3 1- 4-sulpho-2'-methylphenyl-) pyrazolone-S-carboxylic acid-3 1- 2',5'-dichloro-4'-sulphophenyl-) 3 methyl-pyrazolone-S 1- (4-sulphophenyl-) 3-methyl-pyrazolone-S 1- (4-sulpho-2-methyl-) 3-methy1-pyrazolone-5 1- 2',5-disulphophenyl-) 3-methyl-pyrazolone-5 1- (4'-sulphophenyl-) 3 methyl-S-amino-pyrazole If the monoazo dyestulTs obtainable according to the invention still contain diazotisable amino groups, they can be diazotised by a conventional method and again reacted with a suitable coupling component to produce disazo dyestuffs. Another possibility of synthetising diazo dyestuffs consists in preparing monoazo dyestuffs which still contain coupling positions and to combine them with suitable diazo components, the aminobenzothiazole-diazo components carrying a reactive sulphonyl substituent in the 2-position, which are to be used according to the invention, being employed for the first or second, or also for a later coupling step.

As azo components serving for the synthesis of the monoazo dyestuffs there are chiefly used those of the 6 EXAMPLE 1 13.2 parts 2-methylsulphonyl-6-amino-benzothiazole are stirred in 100 parts by volume ice-water and 16 parts by volume concentrated hydrochloric acid; a solution of 5 4.1 parts sodium nitrite in 10 parts by volume water is 21 5 g g gg gg zgi ggziggggggggg and added thereto in one jet. The diazo compound dissolves As g 2 e uent dial com onnt f r the with a yellow colour. After removal of the excess nitrous S nthes.s 3 disazo f there g be f acid, the diazo solution is added'to a solution of 17.6 y 1 y y parts Z-hydroxynaphthalene-3,6-disulphonic acid and 1-aminobenzene-2,3 and -4-sulphonic acid 10 parts sodium carbonate in 200 parts ice-water. The con- 1-aminobenzene-2,4-disulph0nic acid pling is rapidly completed. The dyestufi filtered off with 1-aminobenzene-2,S-disulphonic acid suction and dried at 50. A red powder is obtained. In 1-amino-2-hydroxybenzene-3,S-disulphonic acid the form of the free sulphonic acid the resultant dyestuff l-amino-2-hydroxybenzene-5 -sulphonic acid 1 corresponds to the following formua: 1-amino-2-hydroxy-3-chlorobenzene-5-sulphonic acid 5 N 1-amino-2-hydroxy-3-nitrobenzene-S-sulphonic acid OH 50311 l-aminonaphthalene-l,S-disulphonic acid CH3502 I I Z-aminonaphthalene-l-sulphonic acid S and those of the series of 4,5,6- and 7-amino-2-methylsulphonyl-benzothiazoles. Diazo components of this group can also be used twice. 03H

If the dyestuffs produced according to the invention contain groups forming metal complexes, they can be The dyestuff dyes cellulose in red shades of very good transformed into their 1:1 or 1:2 metal complex comfasineso propeftles, especially y good faStIleSS [0 pounds by the reaction with metal-yielding agents, for exprooosslngample, copper, nickel, chromium or cobalt salts. When a p o analogous to {i116 mothod 0f t The groups forming metal complexes can be intropresent example is followed, but with the use of the duced, for example, by combining diazo components with Components llstod the followlng table, Teaotlve y azo components and choosing the components so that Stufis are also obtained, Whlch, when PP y one of the azo group stands between two o-positioned groups the usual methods, yield fast dyeings the shades of which forming metal complexes, such as hydroxyl groups. Alare also stated in the table.

Diazo component Coupling compojent Shade Number:

2 Q-methylsulphonyl-G-amino-benzothiazole- 2-hydroxynaphthalene-6,8-disulphonic acid" Yellow. 3 "do 1-hydroxy-8-benzoylaminonaphthalenea,5- Red.

- disulphonic acid. 4 do l-hydroxy-S-acety1aminonaphthalene-3,5- Red.

disulphonic acid. 5 do 1-hydroxy-8-acetylaminonaphthalene-3,6- Bluish red.

disulphonic acid. 6.- l-hydroxynaphthalene-4,7-disulphonic acid Scarlet. 7. d l hydroxynaphthalene4,8-disulphonic acid Do. 8 7-methyl-6amino-2-methylsulphonyl-benzo- 1-hydroxy-B-acetylaminonaphthalene-3,6- Red.

thiazole. disulphonic acid. 9 tstullphoifi'amino-2-methylsulphony1-benzodo Red.

IEZO e. 10 fi-aiilil inoifi-methoxy-2-methylsu1pho11ylbenz- 2-hydroxynaphthalene3,6-disulphonic acid. Red.

12.20 e. 11 5arkninoifi-methoxy-2-methylsulphonylbenz- .do Red.

1320 e. 12 6-amino-7-r'nethoxy-2-methylsulphonylbenz- ..-.do Red.

thiazole. 13 6-amino-5-sulpho-2-methylsu1phonylbenzdo Red.

thiazole.

ternatively, it is also possible to introduce, in addition to EXAMPLE 14 a hydroxyl group alre ady present, a second hydroxyl group by the method of oxidative coppering, and thus to build up metal complexes. The lastmentioned process permits to obtain metal complexes also from monoazo dyestuffs containing 4,5,6- or 7-amino-2-methylsulphonylbenzothiazole as diazo component.

The new dyestuffs are extremely valuable products which are suitable for a great variety of applications. The Water-soluble dyestuffs, especially those containing sulphonic acid groups, are interesting mainly for the dyeing of textile material containing hydroxyl groups or nitrogen, especially textile materials of natural and regenerated cellulose, and also of wool, silk, synthetic polyamide and polyurethane fibres. Due to the reactive sulphonyl substituent(s) in the 2-position of the thiazole ring, these products are especially suitable as reactive dyestufis for the dyeing of cellulose materials by the methods known for this purpose. The fastness properties achieved are excellent, particularly the fastness to wet processing. The high yield of the new reactive dyestuffs is also Worth mentioning.

In .the following examples which are given for the purpose of illustrating the invention, the parts stand for parts by weight, unless otherwise stated; the temperatures are given in degrees centigrate.

When a cellulose fabric is printed with a printing paste containing, per kilogram, 10 g. of the dyestuff, g. urea, 300 ml. water, 500 g. alginate thickener (60 g. sodium alginate per kg. thickener) and 10 g. sodium carbonate, and which has been made up to 1 kg. with water,

the fabric is then dried, steamed at 105 for 1 minute, H NHZ rinsed with hot Water and soaped at the boil, an intense S reddish yellow print of good fastness to wet processing N=N and light is obtamed. 802cm When the procedure described in the present example is 5 HO3S followed, but with the use of the diazo and coupling 1 N components listed in the following table, valuable re- SOQH active dyestuffs are also obtained.

Diazo component Coupling component Shade Number:

2-methylsulphonyl-6amino-benzoth1azole 1-(3-S11lphophenyl)-3-methyl-pyrazolone-5 Yellow. 16 do 1-(2,5-dichloro-4-sulpho-phenyl)-3-methyl- Do.

pyrazolone-5. 17 d0 1(4-sulph0phenyl)-3-methyl-pyrazolone-5. Do. 18 d0 1-(2-methyl-4-sulphophenyl)-3-methyl- Do.

pyrazolone-5. 19 6amino-5-methoxy-2-methylsulphonyl- 1-(4-sulphophenyl)-pyrazolone-(5)-3-carbox- Do.

benzthiazole. ylic acid. 20 5-amino-6-methoxy-2-methylsulphonyl- .do Do.

benzthiazole. 21 fi-amino-5-su1pho-2-methylsulphonyl-benzdo Do.

thiazole.

EXAMPLE 22 A fabric of cotton or regenerated cellulose can be dyed 14 parts Z-methylsulphonyl 6 amino-7-methyl-benzothiazole are stirred with 100 parts by volume ice-water and 16 parts by volume concentrated hydrochloric acid. 4.1 parts sodium nitrite dissolved in a little Water are added in one jet, whereupon an almost clear yellow solution of the diazonium salt is obtained. After destroying the excess nitrite, a neutral solution of 18.5 parts l-hydroxy- 7-aminonaphthalene-3,6-disulphonic acid in 100 parts water is added dropwise; the coupling is completed after stirring for several hours. After filtering off with suction and drying, a red powder is obtained. The dyestutf corresponds to the following formula:

and dyes cellulose in red shades.

The following table gives dyestuifs which are prepared in analogy with the instructions of the present example, but With the use of other starting components.

with this dyestuif in the following manner:

grams cotton skein are dyed in 1 litre of a dyebath containing 1.5 g. of the above dyestufi by raising the temperature from 20 to about 80 within 30 minutes While adding a total of 50 g. sodium chloride in several portions, subsequently adding 20 g. trisodium phosphate and treating the material at the said temperature for minutes. After rinsing, soaping at the boil and drying, a clear navy blue dyeing of good fastness to wet processing, rubbing and light is obtained.

It is also possible to proceed as follows: a cotton fabric is impregnated with a solution at 2025 containing, per litre liquor, 20 g. of the above dyestuif and 0.5 g. of a non-ionic wetting agent (e.g. a polyethoxylated oleyl alcohol), 150 g. urea and 15 g. sodium bicarbonate, and the fabric is subsequently squeezed between two rubber rollers to a moisture content of about 100%. After an intermediate drying at 5060, the fabric is heated at 140 for 10 minutes and the dyeing thus obtained is thoroughly rinsed with hot water and treated at the boil for 20 minutes with a solution containing, per litre, 5 g. Marseilles soap and 2 g. sodium carbonate. After rinsing and drying, an intense navy blue dyeing of good fastness to wet processing, rubbing and light is obtained.

pH value of coupling Diazo component Coupling component medium Shade Number:

23 2-methyl-sulph0nyl-4-sulpho-6-am1no-benzoth1azole 1-l1ydroxy-7-amino-naphthalene-EK-sulphonic acld Mineral acid"..- Red. 24 2-methy1-sulphonyl-fi-ammo-benzotlnazole Z-ammo-naphthalene-5,7-disu1phonic acid Acetic acid Orange,

EXAMPLE 25 60 Similar results are also obtained by proceeding accord- A neutral solution of 18.5 parts 1-hydroxy-8-aminonaphthalene-3,5-disulphonic acid in 100 parts by volume Water is added dropwise to the diazo solution prepared according to the instructions of Example 1 from 6-amino-2- methylsulphonyl-benzothiazole. Coupling is completed after stirring for 2-3 hours. The monoazo dyestuffs is filtered oil with suction, slurried in 100 parts by volume water, neutralised with sodium carbonate and, after the addition of 10 parts sodium carbonate, mixed with a diazo solution prepared from 10.1 parts p-sulphanilic acid. After briefly stirring at 10, the coupling is completed. The dyestutf is separated by the addition of potassium chloride. It is a black powder which dissolves in water with a blue colour. In the form of the free sulphonic acid the dyestuif corresponds to the following formula ing to the first-mentioned method of application (dyeing from a long bath), but carrying out the addition of salt and the after-treatment with trisodium phosphate for one hour at room temperature (2030), instead of at This applies also to the last-mentioned method (pad-dyeing): blue dyeings with the fastness properties mentioned above are also obtained with the use of 15 g. sodium bicarbonate, as stated, or of 10 g. sodium carbonate, instead of 15 g. sodium bicarbonate, and by storing of the cellulose fabric, after squeezing it to a moisture content of at room temperature for 5-20 hours, instead of intermediate drying and heating at The following table gives dyestuffs which are obtained from the stated components in analogy with the method described in Example 25.

TABLE Diazo component for acidic Diazo component for alkaline Shade of dyeing on coupling in o-position to --NH Middle component coupling in o-position to OH cellulose Number:

26 2-methylsulphonyl-6-aminobeizothiazole.

disulphonic acid l-hydroxy-8-amino-naphthalene-3,5-

l-aminobenzene-2-sulphonic acid- Navy blue.

Aminobenzene Do. l-aminobenzene-2,5-disu1phonic acid Do. l-aminobenzene-2,4-disulphonic acid Do. do l-aminobenzeneli-sulphonic acid- Do. i-hydroxy-B-amino-naphthalene-3,6- Aminobenzene Greenish dark-blue.

disulphonic acid. 32 .do do l-aminobenzene-4-sulphonic acid Do. 33 do. d0.. l-aminohenzene-Z-sulphonic acid Do. 34.-. do. i l-aminobenzone-2,4-disulphonic acid Do. 25.-. do l l-aminobenzene-2,5-disulphonicacid- Do. 36 l-aminobenzeneA-sulphonic acid ..do 2-menthylsulphonyl-G-amino- Do.

benzothiazole. benzothiazole. 37" Z-methylsulphonyl-B-aminod 4-amino'azobenzene-3,4-disulphonic Do.

benzthiazole. ac 38 1-amino-benzene-3-sulphonic acid do G-amiuo-sulpho-2-methylsulphonyl- Do.

benzthiazole.

EXAMPLE 39 EXAMPLE 40 18.7 parts of 2-ethylsulphonyl-6-a-mino-benzthiazole-5- sulphonic acid are diazotised. The diazo compound is filtered with suction and the wet paste added to an aqueous neutral solution of 14.7 parts of 1-(4-sulphophenyl)-3- methyl-pyrazolone-S in 500 parts by volume of ice-water. After the addition of sodium acetate a pH value of 4 to 5 is maintained. After completion of the coupling the dyestutf formed is precipitated with of sodium chloride, filtered with suction and dried at 50 C.; it corresponds to the probable formula:

N soar CzH5SO2- -N=N-cm s LL i s'o H The dyestuit dissolves in water with a yellow coloration and dyes cotton according to the processes given in the preceding examples yellow shades having very good wet and light fastness properties.

The diazo componentused in this example can be prepared as follows:

140 parts of Z-ethylsulphonyl-6-amino-benzthiazole are added to 440 parts of sulfuric acid monohydrate. The temperature of the reaction mixture raises from about 20 C. to 70 C. At 70 C. to 80 C. 670 parts of 20% oleum are added dropwise within 1 hour, the reaction mixture then heated to 120 C. and kept at this tempera ture for 1 hour. The reaction temperature is subsequently 18.7 parts of 2-ethylsulphonyl-6-aminobenzthiazole-5- sulphonic acid are diazotised and. the slightly soluble diazo compound filtered with suction. The suspension of the diazo compound is then given to 500 parts of water and treated with a neutral solution of 12.9 parts of 1- arninonaphthalene-6-sulphonic acid. After stirring for several hours in acetic acid medium the coupling is completed. The monoazo dyestuif formed corresponds to the probable formula:

It is again diazotised and coupled in bicarbonate alkaline medium with 17.6 parts of 1-hydroxynaphthalene-4,8-disulphonic acid. After the addition of sodium chloride the disazo dyestuff formed is precipitated. The wet paste is then stirred with 500 parts by volume of Water. parts by volume of 20% sodium acetate solution and 80 parts by volume of 18% of copper sulfate solution are added together with parts by volume of a 3% hydrogen peroxide solution at room temperature. After completion of the oxidative coppering the copper complex dyestuff is precipitated with potassium chloride. It dissolves in water with dark green coloration and dyes cotton according to the processes given in the preceding examples dark green shades with good fastness to light. The dyestufl corresponds to the probable formula N cooled :down to room temperature and the mixture poured O H 0 Cu O S O E into 1300 parts of ice, filtered with suction and washed 3 3 G2I1'5S O2 w1th saturated sodium chloride solution unt1l neutral re- ---N N-- -N=N- act1on of the washing liquor is obtained.

If proceeding according to the process for manufactur- 60 ing the dyestuif in this example but using the starting components given in the following table reactive dyestuffs having similar dyeing properties are obtained. 503B SOKH Diazo component Coupling component Shade 2-ethylsu1phonyLfi-amindbenzthiazole-5sulphonicacid--. 1-(3'-sulphophenyl)*3-rnethyl-pyrazolone-5 Yellow.

Do 1-(2-methyl-4-sul hophenyl)-3-methyl-pyrazolone-5 Do.

Do 1-(4-sulphophenyl -3-carboxy pyrazolone-5 Reddish yellow.

(S OaNa)z HO D0 Ni-phthalocyanine Green.

s OZNH-N J CH2 N 2 11 EXAMPLE 41 14 parts of Z-ethylsulphonyl-fi-amino-benzthiazole are pasted with 200 parts by volume of ice-water and 16 parts by volume of concentrated hydrochloric acid. Into this suspension there is poured a solution of 4.1 parts of sodium nitrite in 10 parts by volume of water. The diazo compound dissolves after short stirring with yellow coloration. Excess nitrite is removed by the addition of amido sulphonic acid. After adding concentrated sodium acetate solution a pH value of 1.5 is kept constant. Then a neutral solution of 18.5 parts of 1-hydroxy-8-aminonaphthalene-3,6-disulphonic acid in 100 parts by volume of water are added dropwise within 1 hour. After further stirring for several hours the acid coupling is finished. The reac- Diazo component Coupling component Shade 2-cthylsulphonyl-Gamino-benzthiazole 2-hydI0xy-napththalene-3,6-disulphonic acid Ruby.

Do Z-hydroxy-naphthalcne-5,7-disulph0nic acid- Do.

Do 2-l1ydr0Xy-11aphthalene-6,8-disulphonic acid Do.

Do. 1-hydr0xy-naphthalene-3,6- or 4,6- or -4,7-disulphonie acid Reddish violet.

Do. 1-hydroxy-naphthalene-3,6,8-trisulphonic acid Violet.

Do. l-hydroxy-6-ureid0-naphthalcne-3,5-disulphonic acid. Ruby.

D0 l-hydroxy-S-acetamino (or benzoylamino)-naphthalene-3,G-disulphonic acid Violet.

Do. l-hydroxy-S-acetamino (or benzoylamino) -naphthalenc 3,5-(1iS1LlphOnio acid- D0.

tion mixture is subsequently neutralized by means of soda and after the further addition of 10 parts of soda treated with the diazonium salt solution prepared from 10.1 parts of 1-aminobenzene-2-sulphonic acid. After completion of the coupling the dyestulf formed is precipitated with the addition of potassium chloride. After drying the dyestuif represents a black powder which dissolves in water with blue coloration. In form of the free acid it corresponds to the probable formula SOsH OH NH:

The dyestuif dyes cotton in accordance with one of the processes described in the preceding examples strong navy blue to black shades having good fastness to wet processing and to rubbing.

If using instead of 1-aminobenzene-Z-sulphonic acid as diazo component in the second coupling reaction the same amount of 1-aminobenzene-3-sulphonic acid Or l-aminobenzene-4-sulphonic acid or the equivalent amount of aniline or 2-amino-naphthalene-1,5-disulphonic acid one likewise obtains valuable reactive dyestuifs which dye cotton strong navy blue to black shades.

EXAMPLE 42 14 parts of 2-ethylsulphonyl-6-aminobenzthiazole are diazotised and the diazo suspension added dropwise to a solution of 17.6 parts of 1-hydroxy-naphthalene-4,8-disulphonic acid and 16 parts of sodium bicarbonate in 200 parts by volume of ice-water. After completion of the coupling 80 parts by volume of a 20% sodium acetate solution as well as 8 0 parts by volume of an 18% copper sulphate solution are added. 200 parts by volume of a 3% hydrogen peroxide solution are then added at room temperature. After completion of the oxidative coppering the copper complex compound is precipitated by means of potassium chloride. After drying at 50 C. one obtains a dark powder which dissolves in water with violet coloration and dyes cotton strong reddish violet shades having good fastness to light and to Wet processing. In form of its free acid the dyestulf corresponds to the probable formula EXAMPLE 43 parts of the trisodium salt of the dyestufi of the probable formula in 300 parts of water are treated at C. and at a pH value of 7 with the 1:1-chromium complex compound of 27.2 parts of the dyestufi of the formula The mixed chromium complex compound thus formed corresponds to the formula Q H0.s I snag) It is precipitated with sodium chloride. The mixed chromium complex dyestuff dyes cotton in accordance with one of the processes given in the preceding examples bluish black shades having excellent fastness to light and to wet processing.

The 1:1-chromium complex compounds and the metal free dyestuffs listed in the following table may likewise be combined to form the unsymmetrical 1:2 mixed chromium complex dyestuffs which exhibit valuable reactive dyestuff properties and which dye cotton black shades.

14 EXAMPLE 45 33.6 parts of 2-phenylsulphonyl-6-aminobenzthiazole are poured with stirring into 200 parts of concentrated 1:1-chromium complex Metal free dyestutf (probable formula) Shade 4-nitro-2-amino-1-hydroxybenzene-G-sulphonie acid l-benzoyl-amino-B- HO NHC CH Black.

hydroxy-naphthalene-it,6disu1phonic acid. N O H l I II C 1H5 S O 2 O S -N=N HOaS \/SaH 4-nitroQ-amino-l-hydroxy-benzene l-benzoylamino-8-hydroxy- HO NH-C C H5 Do.

naphthalene-3,6-disulphonic acid. N O H I H I 02115 s 0 2- 0 S N=N H 0 33 -S 0 3H trnitro-l-amino-2-hydroxy-naphthelene-i-sulphonic acid 2-hydroxy- HO NH-C C 0H Do.

naphthalene. N O H II 0211; s 02 O S -N=N H0 8 -SO H l-amino-2-hydro'xy-naphthalene-4-sulphonic acid 1-benz0yl-amino-8- H O NH-O 0 H Do.

hydroxy-naphthaleue-3,6-disulphonic acid. N

v C 2H5 S O 2 EXAMPLE 44 23.2 parts of 2-methylmercapto-6-amino-benzthiazole arepasted with 100 parts of'ice and 32 parts by volume of concentrated hydrochloric acid; a thick and almost colorless paste of the hydrochloride is thus obtained. The paste-isthendiluted with 100 parts-ofice and a solution .of 8.5 parts, of sodiumnitrite in' little water added at 0-5 C..within the course of 1 to 2 hours. After this time a clear yellow solution of the diazo compound has formed. To this solution further 300 parts of ice are added and subsequently parts of chlorine conducted into the solution with stirring and within about one hour. The chlorine is rapidly absorbed. The reaction mixture is further stirred for 3 to 4 hours while keeping the temperature below 5 C. The main quantity of excess chlorine is blown oil by means of air. The residual amount of chlorine is removed byadding little amounts of sodium sulphite. After clarification the pH of the reaction mixture is adjusted by means of sodium acetate solution to pH 2.

A neutral solution of 34 6.parts of l-amino-8-hydroxynaphthalene-3,6-disulphonic acid in 200 parts by volume of water is added dropwise Within l hour. After completion of the coupling reaction the mixture is neutralized with dilute soda-lye. i

A diazo suspension prepared by diazotisation of 18.8 parts or l-aminobenzene-2-sulphonic acid is added to the above said reacti c'inriiiiitiire. when" the second coupling step is complete the solution is heated to C. and the disazo. dyestutfprecipitated. with 20% of potassium chloride calculatedon the volume of the reaction mixture. The product obtained is filtered with suction and dried at C. Inform'of-its-free sulphonic acid the dyestuff corresponds to the formula S0 11 OH NH2 given in the preceding examples greenish-blue to black shades having good fasteness properties.

sulfuric acid at 0 to 10 C. When the component has completely dissolved 38 parts of a 43.3 nitrosyl sulfuric acid are added dropwise at 0 to 10 C. The reaction mixture is stirred in an ice-bath for about 1 hour and then 400 parts of ice added and the initially clear solution treated with 40 parts of calcinated sodium sulfate. The diazo compound thus formed precipitates after short stirring as a thick crystal slurry which is filtered with suction and washed with little saturated sodium chloride solution.

The diazo compound obtained according to the above mentioned process is stirred with 400 parts of ice-water and adjusted to a pH of 1.5 by the addition of crystalline sodium acetate. To this diazo suspension a neutral solution of 37 parts of 1-hydroxy-8-amino-naphthalene-3,6-disulphonic acid in 200 parts of water are added dropwise.

After several hours the acid coupling is complete. The reaction mixture is then neutralized by dropwise adding dilute soda-lye. It is diluted with ice-water and there are then added 20 parts of soda and the diazo suspension obtained from diazotisation of 20.2 parts of l-aminobenzene- 2-sulphonic acid. After completion of the second coupling step the disazo dyestuff obtained is precipitated at 40- 50 C. by the addition of sodium chloride. After drying at 50 C. the dyestufi? represents a bluish black powder which dissolves in water with blue coloration. In form of its free sulphonic acid the.dyestufi corresponds to the formula stufls are obtained which are likewise distinguished by their good fastness properties.

3,480,611 15 16 2- 4'-methylphenylsulpl1onyl) -6-amino-benzthiazole N 2- (4'-chlorophenylsulphonyl) -6-amino-benzthiazole on 2-(3-carboxyphenylsulphonyl)-6-amino-benzthiazo1e cH3SO2 I EXAMPLE 46 O s I I The diazonium salt solution prepared in accordance 5 N with Example 1 from 23.4 parts of 6-amino 2 methyl It 011 sulphonyl-benzthiazole are added to a solution of 10.7 I parts of 3 amino 1 methylbenzene (as hydrochloride) Ho in 50 parts of water. The monoazo dyestuff formed is 10 a precipitated and filtered with suction and the filter residue Washed with dilute hydrochloric acid. The monoazo com- SOKH poun is then pasted with 400 parts of formamide, 20 It dyes cotton brown shades. parts of concentrated hydrochloric acid and 6.9 parts of sodium nitrite added. The diazo azo compound thus pre- EXAMPLE 48 pared is then given to a solution of 38.4 parts of l-hy- Parts Of z-methylsulphonyl 6 benlthiazole are droxynaphthalene-3,6,8-trisulphonic acid in 1500 parts of diazotized. The diazotisation mixture is added dropwise Water. The pH value of the reaction mixture is kept at 8 to a solution of 20.9 parts of 1 hydroxy-8-acetylamin oby the addition of a suspension of calcium hydroxide in naphthalene 3,6-disulphonic acid and 10 parts of soda water. After 2 hours reaction time the precipitated disazo in 100 parts of ice-water. After completion of the coupling dyestufi' is salted out by the addition of 20% of rock salt, the dyestuif is salted out with sodium chloride and the calculated on the volume of the reaction mixture. The precipitated dyestufi filtered with suction. precipitated dyestufi is filtered with suction and the filter The dyestuif paste thus obtained is hot dissolved in residue again dissolved in 1500 parts of water and treated 1000 parts by volume of Water and 80 parts by volume with grams of crystaline copper sulfate. At a pH of 25 of a 20% sodium acetate solution as well as 80 parts by 5-6 and at 25 C. 55 parts of a 15% solution of hydrovolume of a 18% copper sulphate solution added. About gene peroxide are added dropwise within 1 hour, a blue 160 parts by volume of a 3% hydrogene peroxide solusolution thus being formed. After completion of the oxytion are added at a pH of 5-6 and at a temperature of dative coppering the copper complex dyestufi is precipi- 5060 C. within 1 hour. When the oxydative coppering tated by the addition of 20% of rock salt calculated on is complete the copper complex dyestufi formed is prethe volume of the mixture, filtered with suction and dried cipitated by the addition of sodium chloride and isolated. at 50 C. The dyestutf dyes cotton blue shades with good After drying at 50 C; one obtains a dark powder which fasteness properties. dissolves in water with a violet coloration and which dyes If in this example the starting components are replaced cotton according to one of the processes given in the preby those of the following table, valuable fibre reactive ceding examples violet shade. In form of its free sulcopper complex diazo dyestuffs are likewise obtained phonic acid the dyestuif corresponds to the probable which dye cotton in the shades listed below. formula 1 Diazo component 2. Diazo component Azo component Shade 6amino-2-methyl-sulphonyl-benzthiazole 1amino-3-hydroxy-acetyl-amlno-henzene 1-hydroxynaphthalenc-3,6,8-trisulphonic acid Blue. 6amigo-5-sulpho-2-mothylsulphonyl benzthil-amino-naphthalene-osulphonic acid do Do. 5 iiiiflo-6-sulpho-2-mcthylsulphonyl-benzthido ..d0 Do.

X A N E MPLE 47 OCu0 NHCOOH 26.2 parts of the dyestulf of the formula C sSOr- I I 50 N=N O Cu-0 S ijsour H033 HO N=N- S0311 If in this example the starting components are replaced by the diazo and azo components given in the following table similar fibre reactive copper dyestuffs are obtained SOSH which dye cotton in the shades indicated below.

Shade of copper Diazo component Azo component complex 2-methylsulphonyl-G-amino-benzthiazole l-hydroxy-naphthalene-4,8-disulphonic acid Violet. Do 2-hydroxy-naphthalene-3,fi-dusulphonic acid Ruby. Do 1-(4sulphophenyl)-pyrazolon-(5)-carboxlyic acid-3 Yellow brown are dissolved neutral in 200 parts by volume of water We claim: and a diazo solution prepared from 13.3 parts of 2- 1. The dyestufi of the formula methylsulphonyl 6 amino-benzthiazole added. The R coupling is completed by the further addition of sodium N acetate and the dyestulf is precipitated by means of sodium 1 chloride. After filtering with suction and drying at 50 C. N:N A one obtains a dark brown powder which dissolves in J water with brown coloration. In form of the free sul- S n phonic acid the dyestuif corresponds to the formula wherein A is selected from the group consisting of I nickel phthalocyanine wherein R is selected from the group consisting of hydrogen, methyl, sulfonic acid, carboxylic acid, halogen, hydroxy, methoxy, cyano, and sulfonamide; 'R is selected from the group consisting of lower alkyl containing one to five carbon atoms, phenyl, chloro-phenyl, methyl phenyl, carboxy phenyl, benzyl, tolyl methyl, and benzothiazole-2-yl; B is selected from the, group consisting of hydrogen, lower alkoxy, acetamino, benzoyl amino, phenylamino and sulfophenylamino; C 'is selected from the group consisting of-hydrogen, chlorine, bromine, and methyl; D is selected from the group consisting of hydrogen, hydroxy, acetamino and. benzoyl amino; E is a diazo residue derived from compounds selected from the group consisting of l-aminobenzene-Zfi and 4-sulfonic acid, 1-aminobenzene-2,4-disulfonic acid, 1-aminobenzene-2,5-disu1fonic acid, 1-amino-2-hydroxybenzene-3,5- disulfonic acid, 1-amino-2-hydroxybenzene-5-sulfonic acid, 1-amino-2-hydroxy-3-chlorobenzene-5-sulfonic acid, 1 amino 2-hydroxy-3-nitrobenzene-5-sulfonic acid, 2- amino naphthalene-1,5-disulfonic acid, Z-amino napthalene-l-sulfonic acid, and 4, 5, 6 or 7-amino-2-methylsulfonyl-benzothiazole; G is selected from the group consisting of acetyl and benzoyl; X stands for 0 or NH; K and K are selected from the group consisting of hydrogen, methyl, methoxy, acetamino, benzoyl amino and w-methane sulfonic acid; u stands for a number from one to three; t stands for a number from one to two; w stands for a number from one to three; and n stands for a number from one to two.

2. A dyestutf according to claim 1 wherein A is further selected from the group consisting of wherein the two linkages in the condensed benzene ring of the benzothiazole compound are in the o'rtho position relative to Oneanother.

3. A dyestufi' of claim 1 corresponding to the formula SOQH OH NHg 1 9 2O 4. A dyestutf of claim 1 corresponding to the formula 10. A dyestuif of claim 1 corresponding to the formula OH NH: 1 S S N=N N=N 5 -N=N CH3 /SOzC2H5 C2I'I5SO2\ H0 8- -s0 H -so H HO 3 I 3 N N 3 5. A dyestulf of claim 1 corresponding to the formula O O SOBH NH SQzlnickelphthalocyaIune] 11. A dyestuff of claim 1 corresponding to the formula 6. A dyestuff of claim 1 corresponding to the formula 12. A dyestuff of claim 1 corresponding to the formula 7. A dyestuff of claim 1 corresponding to the formula SOaH C zHaS 02x H O S 0 3H 8. A dyestuff of claim 1 corresponding to the formula CzH SOn- HOaS S 0311 N=N c11 CaHaSOz H I-IO 13. A dyesturf corresponding to the formula c1 N\ 01 oH;s0i I N=N soar! S0311 S 9. A dyestuff of claim 1 corresponding to the formula sc n 14. A dyestufi corresponding to the formula 5 N=N --o0oH C:H5SO3- i I soar; HO f N N i on NHCCH;

I 3 l I l N=N s l r soar I soul 21 15. A dyestuff corresponding to the formula H n? H01 /L' O 16. A dyestuif corresponding to the formula OH NHQ SOaH 22 References Cited UNITED STATES PATENTS 3/1957 Straley et a1. 260158 4/1966 Hall et a1. 260-158 XR FOREIGN PATENTS 4/ 1964 Great Britain. 3/1962 France.

FLOYD D. HIGEL, Primary Examiner US. Cl. X.R. 

